JP2008218639A - Insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulation film of a semiconductor device that has a uniform film thickness from the center to the outermost periphery section, has low density, and has improved film characteristics of permittivity, Young's modulus, and the like. <P>SOLUTION: The insulation film of a semiconductor device is formed on a substrate by coating and drying a composition, where a polymer compound in which a silsesquioxane cage compound having not less than two unsaturated groups as substituent is polymerized is dissolved in an organic solvent, by a spin-coater to form a film structure and by removing the outer-periphery section of the film structure using a cleaning liquid. In the insulation film of a semiconductor device, the surface tension of the organic solvent is not more than that of the cleaning liquid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an insulating film, and more specifically, an insulating film in a semiconductor element or the like, having an appropriate and uniform thickness from the center to the outermost periphery of the coated surface, and having excellent dielectric constant characteristics, etc. The present invention also relates to an insulating film of a semiconductor device.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a vapor deposition (CVD) method is frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, an interlayer insulating film having a low dielectric constant mainly composed of an organic component called organic spin-on-dielectrics (SOD) has been developed.

  In the coating type insulating film forming process, the insulating film on the outer periphery of the wafer is removed with an organic solvent immediately after coating. This is because in the process after coating, the film on the outermost peripheral portion of the wafer is peeled off, and foreign matter is generated.

  In the process of removing the outer peripheral portion (edge), the bulge generated at the edge after the edge cleaning causes film peeling in chemical mechanical polishing (CMP) in the wiring process. For this reason, in the semiconductor element manufacturing process, an insulating film having a uniform film thickness is required from the center to the outermost periphery.

  Accordingly, the present invention provides an insulating film for a semiconductor device having a uniform film thickness from the center to the outermost periphery, and having a low density and excellent film properties such as dielectric constant and Young's modulus, in order to solve the above-mentioned problems. For the purpose.

The present invention is uniform from the center to the outermost periphery by setting the surface tension of at least one of the organic solvents used as the organic solvent used in the film-forming composition to be equal to or less than the surface tension of the cleaning liquid. The above problem is solved by forming an insulating film having a thickness.
That is, the present invention is as follows.
(1) A composition in which a polymer compound obtained by polymerizing a cage silsesquioxane compound having two or more unsaturated groups as a substituent is dissolved in an organic solvent is applied on a substrate using a spin coater and dried. Forming a film structure and removing an outer peripheral portion of the film structure with a cleaning liquid, wherein the surface tension of the organic solvent is equal to or lower than the surface tension of the cleaning liquid. An insulating film for a semiconductor device.
(2) The insulating film for a semiconductor device according to (1), wherein the cleaning liquid is a ketone-based or ester-based solvent.

  According to the present invention, the film quality is excellent, the film density is low, the film characteristics such as dielectric constant and Young's modulus are excellent, and the film thickness is uniform from the center to the outermost periphery.

  Examples of the cleaning liquid used in the present invention include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate. In addition, ester solvents such as methyl propionate, ethyl propionate, propylene glycol monomethyl ether acetate, γ-butyrolactone, and methyl benzoate, and aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane can be used. Among these solvents, more preferred are ester solvents, among which methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propylene glycol monomethyl ether acetate , Γ-butyrolactone, methyl benzoate, and N-methyl-2-pyrrolidone (NMP), particularly preferably ethyl acetate and butyl acetate. These can be used alone or in combination of two or more.

  For the production of the insulating film of the present invention, a commercially available spin coater equipped with an edge portion removing mechanism can be used. For example, the Tokyo Electron clean truck ACT series can be used.

The insulating film of the present invention uses a polymer compound obtained by polymerizing a cage silsesquioxane compound having two or more unsaturated groups as substituents.
The cage-type silsesquioxane compound having two or more unsaturated groups as a substituent (hereinafter also referred to as compound (I)) is, for example, m RSi (O _0.5 ) ₃ units (m is 8 to 16). Each of R is independently a non-hydrolyzable group, and at least two of R are groups containing a vinyl group or an ethynyl group), and each unit is an oxygen atom in each unit. Examples thereof include compounds that share atoms and are linked to other units to form a cage structure (hereinafter also referred to as compound (I ′)).
For example, m in the compound (I ′) is preferably 8, 10, 12, 14, or 16 from the viewpoint of the effect of decreasing the dielectric constant, and 8, 10, or 12 is more preferable from the viewpoint of availability.

  Here, the cage structure refers to a molecule whose volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot leave the volume without passing through the ring.

  Examples of the cage structure in compound (I) include the following. The free bond in the following represents the position where R is bonded.

Each R independently represents a non-hydrolyzable group.
Here, the non-hydrolyzable group is a group that remains at 95% or more when contacted with 1 equivalent of neutral water at room temperature for 1 hour, but remains at 99% or more under these conditions. Is preferred.
At least two of R are groups containing a vinyl group or an ethynyl group. Examples of non-hydrolyzable groups for R include alkyl groups (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), vinyl groups, ethynyl groups, allyl groups. And silyloxy groups (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) and the like.

Of the groups represented by R, at least two are groups containing a vinyl group or an ethynyl group, but at least two are preferably vinyl groups. When the group represented by R includes a vinyl group or an ethynyl group, the vinyl group or ethynyl group is preferably bonded to the silicon atom to which R is bonded, directly or through a divalent linking group. Examples of the divalent linking group include-[C (R ¹¹ ) (R ¹² )] _k- , -CO-, -O-, -N (R ¹³ )-, -S-, -O-Si (R ¹⁴ ) (R ¹⁵ ) —, and divalent linking groups formed by arbitrarily combining these. (R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and k represents an integer of 1 to 6), among them — [C (R ¹¹ ) (R ¹² )] _k- , -O-, -O-Si (R ¹⁴ ) (R ¹⁵ )-or a divalent linking group formed by arbitrarily combining these is preferable.
In compound (I), the vinyl group or ethynyl group is preferably directly bonded to the silicon atom to which R is bonded.
More preferably, at least two vinyl groups out of R in compound (I) are directly bonded to the silicon atom to which R is bonded, and more preferably at least half of R in compound (I) is a vinyl group. , R are all preferably vinyl groups.

  Specific examples of compound (I) include, but are not limited to, the following.

  Compound (I) may be a commercially available product or may be synthesized by a known method.

  It is also preferable that R in the compound (I) of the present invention is a group represented by the following general formula (II). In this case, the compound represented by the following general formula (III) and the following general formula (IV) It can be synthesized by reacting the compound.

(R ¹ ) ₃ —Si—O— (II)
[MO-Si (O _0.5 ) ₃ ] _m (III)
(R ¹ ) ₃ —Si—Cl (IV)

The compound represented by the general formula (III) can be synthesized according to the method described in, for example, Angew. Chem. Int. Ed. Engl. 1997, 36, No. 7, 743-745.
In these formulas, each R ¹ independently represents a non-hydrolyzable group. Specific examples of the non-hydrolyzable group represented by R ¹ include an alkyl group, an aryl group, a vinyl group, and an ethynyl group. can give. m and R ¹ are the same as in compound (I ′) and general formula (II). M represents a metal atom (for example, Na, K, Cu, Ni, Mn) or an onium cation (for example, tetramethylammonium). When M is a polyvalent metal atom, it means a form in which a plurality of —O—Si (O _0.5 ) ₃ is bonded to the polyvalent metal atom M.

The reaction between the compound represented by the general formula (III) and the compound represented by the general formula (IV) is carried out, for example, in a solvent by combining the compound represented by the general formula (III) and the general formula (III) 1 to 100 times mol of the compound represented by the general formula (IV) of the number of Si-OM groups contained in the compound represented by formula (IV) is added, and the stirring is usually performed at 0 to 180 ° C. for 10 minutes to 20 hours. .
As the solvent, organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable.
When the compound represented by the general formula (III) and the compound represented by the general formula (IV) are reacted, a base such as triethylamine or pyridine may be added.

The composition for forming the insulating film of the present invention (hereinafter also simply referred to as “insulating film forming composition” or “composition of the present invention”) includes a polymer of a plurality of different compounds (I). It may be. In that case, the copolymer which consists of several different compound (I) may be sufficient, and the mixture of a homopolymer may be sufficient. When the composition of the present invention includes a copolymer composed of a plurality of different compounds (I), a copolymer of a mixture of two or more compounds (I ′) selected from m = 8, 10, and 12 It is preferable that
The polymer compound obtained by polymerizing the compound (I) contained in the composition of the present invention may be a copolymer with a compound other than the compound (I). The compound used in that case is preferably a compound having a plurality of polymerizable carbon-carbon unsaturated bonds or SiH groups. Examples of preferred compounds include vinyl silanes, vinyl siloxanes, phenylacetylenes, [(HSiO _0.5 ) ₃ ] _{8 and the} like.
The composition of the present invention is a solution in which a polymer compound obtained by polymerizing compound (I) is dissolved in an organic solvent.
Of the solids contained in the composition of the present invention, the total amount of the polymer obtained by reacting the compounds (I) is preferably 70% by mass or more, preferably 80% by mass or more, and 90% by mass. More preferably, it is more preferably 95% by mass or more.
The higher these contents in the solid content, the lower the density, refractive index and dielectric constant film can be formed.
The solid content mentioned here is a component obtained by removing volatile components from all components contained in the composition. Volatile components also include components that volatilize after being decomposed into low molecular weight compounds. Examples of the volatile component include water, an organic solvent, a hole-decomposing heat-decomposable polymer, and a heat-releasing substituent.
As a component other than the polymer obtained by reacting the compounds (I) contained in the solid content of the composition of the present invention, the compound contained in the copolymer (I) and a copolymer containing the reaction product of the compound (I) Ingredients other than the reactant (I), non-volatile additives and the like can be mentioned.
Compound (I) can be quantified from a solid GPC chart, HPLC chart, NMR spectrum, UV spectrum, IR spectrum, and the like. The components in the copolymer may be determined by the charge ratio, but it can also be determined by measuring the NMR spectrum, UV spectrum, IR spectrum, elemental composition, etc. after purifying the solids as necessary. it can.
For non-volatile additives, a method of using the added amount as an abundance in the solid content, a GPC chart of the solid material, and a method of quantifying from the HPLC chart are possible, but after purifying the solid content as necessary, It can also be quantified by measuring NMR spectrum, UV spectrum, IR spectrum, elemental composition and the like.
What remove | excluding these from solid content is the polymer which compound (I) reacted.

In order to form a film having a good coated surface and a small film loss during firing, it is preferable that the unreacted compound (I) in the solid content contained in the composition of the present invention is small.
The compound (I) in the solid content is 15% by mass or less, preferably 10% by mass or less, and most preferably 5% by mass or less.
The number average molecular weight (Mn) of the portion excluding the compound (I) from the solid GPC chart contained in the composition of the present invention is preferably 20,000 to 200,000, but is 25,000 to 150,000. More preferably, it is more preferably 30,000 to 100,000.
As the number average molecular weight increases, a film having a lower density, refractive index, and dielectric constant can be formed.
In addition, the GPC polystyrene conversion value in this application uses Waters2695 and Shodex GPC column KF-805L, column temperature is 40 degreeC, tetrahydrofuran is used as an elution solvent at the flow volume of 1 ml / min, and sample concentration is 0.5 mass%. 50 μl of terahydrofuran solution was injected, a monomer calibration curve was prepared using the integral value of the RI detector (Waters 2414), the monomer in the solid content was quantified, M _n , M _w and M _{Z + 1} Is a value calculated using a calibration curve prepared using standard polystyrene.
The Z + 1 average molecular weight (M _{Z + 1} ) of the portion excluding the compound (I) monomer from the solid GPC chart contained in the composition of the present invention is preferably 90,000 to 600,000, but 120,000 to 45. 10,000 is preferred, and 150,000 to 300,000 is most preferred.
When the Z + 1 average molecular weight is large, the solubility of the composition in an organic solvent and the filter filterability are deteriorated, and the surface state of the coating film is deteriorated.
If these average molecular weights are in the above range, the coated film has good surface shape, low density and low dielectric constant, good solubility in organic solvents and filter filterability, good surface shape, low density and A composition capable of producing a coating film having a low dielectric constant is obtained.
The Mw of the portion excluding the compound (I) monomer from the solid GPC chart contained in the composition of the present invention is preferably from 30,000 to 210,000, but from 40,000 to 180,000, More preferably, it is 50,000 to 160,000.
From the viewpoints of solubility in organic solvents, filter filterability, and coating film surface conditions, the polymer of the present invention preferably contains substantially no component having a molecular weight of 3 million or more, and substantially does not contain 2 million or more components. It is more preferable that it contains no more than 1 million components.

In the solid content contained in the composition of the present invention, 10 to 90 mol% of the vinyl group or ethynyl group of compound (I) preferably remains unreacted, and 20 to 80 mol% is unreacted. It is preferable to remain in the reaction, and it is most preferable that 30 to 70 mol% remain unreacted.
Moreover, 0.1-40 mass% of polymerization initiators, additives or polymerization solvents may be bonded to the reaction product of the compound (I) in the composition of the present invention. % By mass is preferable, 0.1 to 10% by mass is more preferable, and 0.1 to 5% by mass is most preferable.
About these, it can quantify from the NMR spectrum etc. of a composition.

As a method for producing the composition of the present invention, the reaction product of compound (I) is preferably produced using a polymerization reaction between carbon-carbon unsaturated bonds.
In particular, it is particularly preferred that compound (I) is dissolved in a solvent and a polymerization initiator is added to react the vinyl group or ethynyl group.
The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, and transition metal catalyst polymerization.
The compound (I) remaining at the end of the polymerization reaction is preferably 25% by mass or less, more preferably 20% by mass or less, and most preferably 15% by mass or less of the addition amount. If this condition is satisfied at the time of polymerization, a film-forming composition having a good coated surface shape and a small film loss at the time of firing can be produced with a high yield.
The weight average molecular weight (Mw) of the polymer at the end of the polymerization reaction is more preferably 30,000 to 160,000, further preferably 40,000 to 140,000, and most preferably 50,000 to 120,000.
The Z + 1 average molecular weight (M _{Z + 1} ) of the polymer at the end of the polymerization reaction is preferably 90,000 to 700,000, more preferably 120,000 to 550,000, and most preferably 150,000 to 400,000 preferable.
The polymer at the end of the polymerization reaction is preferably substantially free of components having a molecular weight of 3 million or more, more preferably substantially free of components of 2 million or more, and no components of 1 million or more. Is most preferred.
When these molecular weight conditions are satisfied during polymerization, a film-forming composition that is soluble in an organic solvent, has good filter filterability, and can form a low-density, low-dielectric constant film can be produced.

In order to satisfy the above molecular weight condition, the concentration of the compound (I) during the polymerization reaction is preferably 12% by mass or less. The concentration of compound (I) is more preferably 10% by mass or less, further preferably 8% by mass or less, and most preferably 6% by mass or less.
From the viewpoint of productivity during the reaction, the higher the concentration of compound (I) during polymerization, the more advantageous. In that sense, the concentration of compound (I) during polymerization is 0.1% by mass or more, more preferably 1% by mass or more.

Moreover, after polymerizing the compound (I), the composition of the present invention can also be produced by treating with a method such as removing high molecular weight components by filtration or centrifugation, and purifying using column chromatography. Preferred as a method.
In particular, it is possible to increase the Mn and reduce the amount of the remaining compound (I) by performing reprecipitation treatment on the solid produced by the polymerization reaction and removing the low molecular weight component and the remaining compound (I). A preferred method for producing the composition of the invention.
Here, the reprecipitation treatment refers to adding a poor solvent (a solvent that does not substantially dissolve the composition of the present invention) to the reaction solution obtained by distilling off the reaction solvent as necessary, or adding a reaction solvent as necessary. The distilled reaction solution is dropped into a poor solvent, and after the solid content is dissolved in a good solvent, the composition of the present invention is precipitated by a method such as adding the poor solvent, and this is filtered. .
As the good solvent, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, tetrahydrofuran and the like are preferable, and as the poor solvent, alcohols (methanol, ethanol, isopropyl alcohol) hydrocarbons (hexane, heptane), water and the like are preferable. As the good solvent, it is preferable to use an equal mass to 50 times mass of the composition of the present invention, and it is more preferable to use 2 times mass to 20 times mass. As the poor solvent, it is preferable to use an equal mass to 200 times mass of the composition of the present invention, and it is more preferable to use 2 times to 50 times the mass.

The polymerization reaction of compound (I) is preferably performed in the presence of a nonmetallic polymerization initiator. For example, polymerization can be carried out in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferably used.

  Examples of the organic peroxide include ketone peroxides such as perhexa H, peroxyketals such as perhexa TMH, hydroperoxides such as perbutyl H-69, park mill D, perbutyl C, etc. , Dialkyl peroxides such as perbutyl D, diacyl peroxides such as niper BW, peroxyesters such as perbutyl Z and perbutyl L, peroxydicarbonates such as perroyl TCP, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methyl Benzoyl) peroxide, t-butylperoxy-2-ethylhexanoe , Di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1 , 1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2, , 2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5 , -Trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisop Propyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di-t-butylperoxyvalerate, di (2-t-butylperoxy) Isopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Syn-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, 2,4-dichlorobenzoyl peroxide, o-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, tris- (t-butylperoxy) triazine, 2,4,4-trimethylpentylperoxyneodecanoate, α -Cumylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyl Adipate, di-3-methoxy Butyl peroxydicarbonate, di-isopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, diethylene glycol bis (t-butyl peroxycarbonate), t -Hexyl peroxyneodecanoate, Luperox 11 commercially available from Arkema Yoshitsugu, etc. are preferably used.

  As organic azo compounds, azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70, which are commercially available from Wako Pure Chemical Industries, Ltd., VA-080, Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidine compounds such as V-50 and VA-057 Azo ester compounds such as V-601 and V-401, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2 , 2-azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonite) Ryl), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide }, 2,2-azobis [2-methyl-N- (2-hydroxybutyl) propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-butyl-2-methylpropionamide), 2,2-azobis (N-cyclohexyl-2-methylpropioamide), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydro Chloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2-azobis {2- [1- (2-hydroxy Ethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2-azobis [2- [2-imidazolin-2-yl] propane], 2,2-azobis (1-imino-1-pyrrolidino- 2-methylpropane) dihydrochloride, 2,2-azobis (2-methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, dimethyl 2 , 2-azobis (2-methylpropionate), 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane) and the like are preferably used.

The polymerization initiator is preferably an organic azo compound in view of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction, and most preferably an azo ester compound such as V-601 which does not incorporate harmful cyano into the polymer.
The 10-hour half-life temperature of the polymerization initiator is preferably 100 ° C. or lower. If the 10-hour half-life temperature is 100 ° C. or lower, it is easy to prevent the polymerization initiator from remaining at the end of the reaction.
The polymerization initiator of the present invention may be used alone or in combination of two or more.
The amount of the polymerization initiator used in the present invention is preferably 0.0001 to 2 mol, more preferably 0.003 to 1 mol, and particularly preferably 0.001 to 0.5 mol with respect to 1 mol of the monomer.

Any solvent can be used for the polymerization reaction as long as it can dissolve the compound (I) at a necessary concentration and does not adversely affect the properties of the film formed from the polymer obtained. Also good. In the following description, for example, an ester solvent is a solvent having an ester group in the molecule.
For example, alcohol solvents such as water, methanol, ethanol, propanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, acetic acid Hexyl, methyl propionate, ethyl propionate, propylene glycol monomethyl ether acetate, γ-butyrolactone, ester solvents such as methyl benzoate, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1,2, 4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene Aroma such as 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene Group hydrocarbon solvents, amide solvents such as N-methylpyrrolidinone, dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene And halogen-based solvents such as hexane, heptane, octane and cyclohexane. Among these solvents, more preferred are ester solvents, among which methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propylene glycol monomethyl ether acetate , Γ-butyrolactone and methyl benzoate, particularly preferably ethyl acetate and butyl acetate.
These may be used alone or in admixture of two or more.
The boiling point of the organic solvent is preferably 75 ° C. or higher and 140 ° C. or lower so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction and the organic solvent can be distilled off after completion of the reaction.
The addition method of the polymerization initiator of the present invention includes batch addition, divided addition, continuous addition, etc., but it can be increased in molecular weight with a small addition amount of polymerization initiator and is advantageous from the viewpoint of film strength. And continuous addition is preferred.
In particular, it is possible to maintain the reaction liquid composed of the compound (I) and the organic solvent at a temperature that is at least one hour half the temperature of the polymerization initiator and to add the polymerization initiator in portions or continuously, so that the film strength and the molecular weight reproducibility during the polymerization reaction are increased. From the point of view, it is preferable.

Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, etc., but preferably the internal temperature is 0 ° C. to 200 ° C., more preferably 40 ° C. to 170 ° C., particularly preferably 70. C. to 140.degree. C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

  The composition of the present invention is preferably soluble in an organic solvent. Here, being soluble in an organic solvent means that 5% by mass or more dissolves at 25 ° C. in a solvent selected from cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and γ-butyrolactone. However, it is preferable to dissolve 10% by mass or more, and more preferable to dissolve 20% by mass or more.

In producing the composition of the present invention, the reaction solution obtained by subjecting the compound (I) to the polymerization reaction may be used as it is as the composition of the present invention, but the reaction solvent is distilled off and concentrated for use. Is preferred. Moreover, it is preferable to use after performing a reprecipitation process.
The concentration is preferably carried out by heating and / or reducing the pressure of the reaction solution using a rotary evaporator, a distillation apparatus or a reaction apparatus in which a polymerization reaction is performed. The temperature of the reaction solution at the time of concentration is generally 0 ° C to 180 ° C, preferably 10 ° C to 140 ° C, more preferably 20 ° C to 100 ° C, and most preferably 30 ° C to 60 ° C. The pressure at the time of concentration is generally 0.133 Pa to 100 kPa, preferably 1.33 Pa to 13.3 kPa, and more preferably 1.33 Pa to 1.33 kPa.
When concentrating the reaction solution, it is preferably concentrated until the solid content in the reaction solution becomes 10% by mass or more, more preferably concentrated until it becomes 30% by mass or more, and 50% by mass or more. It is most preferred to concentrate until

  In the composition of the present invention and its production process, a polymerization inhibitor may be added in order to suppress unnecessary polymerization. Examples of the polymerization inhibitor include 4-methoxyphenol and catechol.

  In the present invention, the polymer of compound (I) is preferably used after being dissolved in an appropriate solvent and coated on a support. Solvents that can be used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, mesitylene, Mention may be made of diisopropylbenzene.

  A solution obtained by dissolving the composition of the present invention in a suitable solvent is also included in the scope of the composition of the present invention. The total solid concentration in the solution of the present invention is preferably 1 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 1 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating solution is also more excellent.

The composition of the present invention may contain a polymerization initiator, but it is preferable that no polymerization initiator is contained because the storage stability of the composition is good.
However, when it is necessary to harden the composition of this invention at low temperature, it is preferable to contain the polymerization initiator. Examples of the polymerization initiator in that case include the same ones as described above. For this purpose, it is also possible to use initiators that cause polymerization by radiation.

The composition of the present invention preferably has a sufficiently low metal content as an impurity. The metal concentration of the composition can be measured with high sensitivity by the ICP-MS method, and the metal content other than the transition metal in that case is preferably 30 ppm or less, more preferably 3 ppm or less, and particularly preferably 300 ppb or less. In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the prebaking and thermosetting processes, the content is preferably smaller. Preferably it is 10 ppm or less, More preferably, it is 1 ppm or less, Most preferably, it is 100 ppb or less.
The metal concentration of the composition can also be evaluated by performing total reflection X-ray fluorescence measurement on a film obtained using the composition of the present invention. When W line is used as the X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, each of which is 100 × 10 ¹⁰ cm ⁻² or less. Is more preferably 50 × 10 ¹⁰ cm ⁻² or less, and particularly preferably 10 × 10 ¹⁰ cm ⁻² or less. Moreover, Br which is halogen can also be observed, and the residual amount is preferably 10000 × 10 ¹⁰ cm ⁻² or less, more preferably 1000 × 10 ¹⁰ cm ⁻² or less, and particularly preferably 400 × 10 ¹⁰ cm ⁻² or less. is there. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 ¹⁰ cm ⁻² or less, more preferably 50 × 10 ¹⁰ cm ⁻² or less from the viewpoint of damaging the CVD apparatus, the etching apparatus, and the like. Particularly preferably, it is 10 × 10 ¹⁰ cm ⁻² or less.

  Furthermore, the composition of the present invention includes a radical generator, colloidal silica, and surfactant as long as the properties (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the resulting insulating film are not impaired. In addition, additives such as a silane coupling agent and an adhesive may be added.

  Any colloidal silica may be used in the present invention. For example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, usually having an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 5 to 40% by mass It is.

  Any surfactant may be used in the present invention, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, and fluorine-containing interfaces. Activators, polyalkylene oxide surfactants, and acrylic surfactants can be mentioned. The surfactant used in the present invention may be one type or two or more types. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable.

  The addition amount of the surfactant used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and 0.1% by mass or more and 0.5% by mass or less with respect to the total amount of the film-forming coating solution. More preferably.

  In the present invention, the silicon-based surfactant is a surfactant containing at least one Si atom. The silicon-based surfactant used in the present invention may be any silicon-based surfactant, and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.

In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, x is an integer of 1 to 20, and m and n are each independently an integer of 2 to 100. A plurality of R ¹ may be the same or different.

  Examples of the silicone-based surfactant used in the present invention include BYK306, BYK307 (manufactured by Big Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical). Can be mentioned.

  Any nonionic surfactant may be used as the nonionic surfactant used in the present invention. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.

  As the fluorine-containing surfactant used in the present invention, any fluorine-containing surfactant may be used. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant used in the present invention may be any acrylic surfactant. For example, a (meth) acrylic acid type copolymer etc. are mentioned.

  Any silane coupling agent may be used in the present invention. For example, 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6 -Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, - bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. The silane coupling agent used in the present invention may be one type or two or more types.

  Any adhesion promoter may be used in the present invention. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane , Γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2 -Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldi Ethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzo Triazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, - mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, it may be mentioned thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters. The preferable use amount of the adhesion promoter is preferably 10 parts by mass or less, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content.

In the composition of the present invention, a pore forming factor can be used within the range allowed by the mechanical strength of the film to make the film porous and to reduce the dielectric constant.
There are no particular limitations on the pore-forming factor of the additive that serves as the pore-forming agent, but non-metallic compounds are preferably used, solubility in the solvent used in the film-forming coating solution, and the polymer of the present invention. It is necessary to satisfy the compatibility of

  A polymer can also be used as the pore-forming agent. Examples of the polymer that can be used as the pore-forming agent include polyvinyl aromatic compounds (polystyrene, polyvinyl pyridine, halogenated polyvinyl aromatic compounds, etc.), polyacrylonitrile, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), polyethylene, poly Lactic acid, polysiloxane, polycaprolactone, polycaprolactam, polyurethane, polymethacrylate (such as polymethyl methacrylate) or polymethacrylic acid, polyacrylate (such as polymethyl acrylate) and polyacrylic acid, polydiene (such as polybutadiene and polyisoprene), polyvinyl chloride , Polyacetal, and amine-capped alkylene oxide, other polyphenylene oxide, poly (dimethyl) Siloxane), polytetrahydrofuran, poly cyclohexyl ethylene, polyethyl oxazoline, polyvinyl pyridine, may be a polycaprolactone.

In particular, polystyrene can be suitably used as a pore forming agent. Examples of polystyrene include anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrene (for example, poly (α-methylstyrene)), and unsubstituted polystyrene is preferred.
Further, a thermoplastic polymer can also be used as the pore forming agent. Examples of thermoplastic pore forming polymers include polyacrylate, polymethacrylate, polybutadiene, polyisoprene, polyphenylene oxide, polypropylene oxide, polyethylene oxide, poly (dimethylsiloxane), polytetrahydrofuran, polyethylene, polycyclohexylethylene, polyethyloxazoline. , Polycaprolactone, polylactic acid, polyvinyl pyridine and the like.

Moreover, the boiling point or decomposition temperature of the pore-forming agent is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. As molecular weight, it is preferable that it is 200-50000, More preferably, it is 300-10000, Most preferably, it is 400-5000.
The amount of the pore-forming agent added is preferably 0.5 to 75%, more preferably 0.5 to 30%, and particularly preferably 1% to 20% by mass% with respect to the polymer forming the film. .
The polymer may contain a decomposable group as a pore-forming factor, and the decomposition temperature is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. Good to have. The content of the decomposable group is 0.5 to 75%, more preferably 0.5 to 30%, and particularly preferably 1 to 20% in terms of mol% with respect to the polymer forming the film.

The film-forming composition of the present invention is preferably used for film formation after removing insolubles, gel components and the like by filter filtration. The pore size of the filter used at that time is preferably 0.001 to 0.2 μm, more preferably 0.005 to 0.05 μm, and most preferably 0.005 to 0.03 μm. The material of the filter is preferably PTFE, polyethylene, or nylon, and more preferably polyethylene or nylon.
The film obtained by using the film forming composition of the present invention can be obtained by any method such as spin coating method, roller coating method, dip coating method, scanning method, spray method, bar coating method. After applying to a substrate such as a silicon wafer, a SiO ₂ wafer, a SiN wafer, glass, or a plastic film, the solvent can be removed by heat treatment as necessary. As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, a clean track series (manufactured by Tokyo Electron), a D-spin series (manufactured by Dainippon Screen), an SS series or a CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. The spin coating conditions may be any rotational speed, but a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate from the viewpoint of in-plane uniformity of the film. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate. The heat treatment method is not particularly limited, but generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. Can do. A heating method using hot plate heating or furnace is preferable. A commercially available apparatus can be preferably used as the hot plate, and a clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

  The polymer of the present invention is preferably hardened after being coated on a substrate. Hardened means that the composition on the substrate is cured and the film is given solvent resistance. As a method of hardening, it is particularly preferable to perform heat treatment (firing). For example, a polymerization reaction during post-heating of vinyl groups remaining in the polymer can be used. The conditions for this post-heat treatment are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 1 minute to 2 hours, more preferably 10 minutes to 1.5 ° C. Time, particularly preferably in the range of 30 minutes to 1 hour. The post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.

In the present invention, the film may be hardened by causing a polymerization reaction of a vinyl group or an ethynyl group remaining in the polymer by irradiating with a high energy ray instead of heat treatment. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0 to 50 keV, more preferably 0 to 30 keV, and particularly preferably 0 to 20 keV. The total dose of the electron beam is preferably 0 to 5 μC / cm ² , more preferably 0 to ² μC / cm ² , and particularly preferably 0 to 1 μC / cm ² . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 450 ° C, more preferably 0 to 400 ° C, and particularly preferably 0 to 350 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation in the present invention may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.
Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.

The film may be hardened by performing heat treatment and high energy ray treatment irradiation simultaneously or sequentially.
The film thickness when forming the insulating film is a dry film thickness of about 0.05 to 1.5 μm in thickness when applied once, and about 0.1 to 3 μm in thickness when applied twice. Can do.
Since the cage structure does not decompose during firing, it is preferable that groups (hydroxyl groups, silanol groups, etc.) that undergo nucleophilic attack on Si atoms are not substantially present during the production of the composition and the insulating film.

  More specifically, the composition of the present invention is applied onto a substrate (usually a substrate having a metal wiring) by, for example, a spin coating method, a pre-heat treatment is performed to dry the solvent, and then 300 ° C. to 430 ° C. An insulating film having a low dielectric constant can be formed by performing a final heat treatment (annealing) at a temperature of ℃ or less.

  When the film obtained by using the film forming composition of the present invention is used as an interlayer insulating film for a semiconductor, the wiring structure thereof may have a barrier layer for preventing metal migration on the wiring side surface. In addition, there may be an etching stopper layer, etc. in addition to a cap layer and interlayer adhesion layer that prevent peeling by CMP on the bottom surface of the upper surface of the wiring and interlayer insulating film, and other layers of the interlayer insulating film may be added as necessary. The seed material may be divided into a plurality of layers.

  The insulating film of the present invention may be used by forming a laminated structure with other Si-containing insulating films or organic films. It is preferable to use it laminated with a hydrocarbon film.

  The film obtained using the film forming composition of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. These plasmas can use not only Ar but also oxygen, or gases such as nitrogen, hydrogen, and helium. In addition, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used for the processing, and further, cleaning can be performed to remove a residue at the time of ashing.

  The film obtained using the film forming composition of the present invention can be subjected to CMP (Chemical Mechanical Polishing) in order to planarize the copper plating portion after the copper wiring processing. As the CMP slurry (chemical solution), a commercially available slurry (for example, manufactured by Fujimi, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical, etc.) can be used as appropriate. Moreover, as a CMP apparatus, a commercially available apparatus (Applied Materials Co., Ltd., Ebara Corporation, etc.) can be used suitably. Further, cleaning can be performed to remove slurry residues after CMP.

  The film obtained using the film forming composition of the present invention can be used for various purposes. For example, it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, interlayer insulating film for semiconductor, etching stopper film, surface protection In addition to films, buffer coat films, LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. I can do it. It can also be used as a surface protective film, an antireflection film, or a retardation film for optical devices.

  By this method, an insulating film having a low dielectric constant, that is, an insulating film having a relative dielectric constant of 2.5 or less, preferably 2.3 or less can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis Example 1]
H ₂ C═CH—Si (O _0.5 ) ₃ units of cage-like silsesquioxane, H ₂ C═CH—Si (O _0.5 ) ₃ units of 10 units of cage silsesquioxane and H _{2 C = CH-Si (O 0.5} ) 3 mixture of cage-like silsesquioxane composed of the unit 12 (hybrid plastics Co., model number: OL1170) 1g was added to ethyl acetate 361 g, it was heated under reflux in a stream of nitrogen ( Internal temperature 78 ° C.). As a polymerization initiator, a solution obtained by diluting 4 μl of Lupelox 11 (10 hours half-life temperature 58 ° C.) manufactured by Arkema Yoshitake Co., Ltd. with 4 ml of ethyl acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was heated to reflux for 2 hours, cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol, stirred for 1 hour, filtered and dried to obtain 0.95 g of a solid content. This was dissolved in 15 ml of tetrahydrofuran, and 5.5 ml of water was added dropwise with stirring. After stirring for 1 hour, it was collected by filtration and dried to obtain 0.52 g of a solid content. When the solid content is analyzed by GPC, the components having a molecular weight larger than that of the mixture of the starting cage-like silsesquioxane are M _n = 51,000, M _w = 138,000, M _{z + 1} = 370,000. There was no component with a molecular weight of 3 million or more. The unreacted starting material in the solid was 3% by mass or less. As GPC, Waters 2695 and Shodex GPC column KF-805L are used, column temperature is 40 ° C., tetrahydrofuran is used as an elution solvent at a flow rate of 1 ml / min, and a terahydrohydrofuran solution having a sample concentration of 0.5 mass%. Was injected. A monomer calibration curve was created using the integrated value of the RI detector (Waters 2414), and the monomer in the solid content was quantified. M _n , M _w and M _{Z + 1} were calculated using a calibration curve prepared using standard polystyrene.
When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerizing the vinyl group and the remaining proton peak derived from the vinyl group had an integration of 43:57. The ratio was observed and it was found that vinyl groups were polymerized.
When 0.3 ml of this composition was added with 5 ml of a coating solvent (described in Table 1) and stirred at 40 ° C. for 3 hours, it was uniformly dissolved to obtain composition A.
From the weight of the remaining monomer and the weight of the additive, it is clear that the polymer obtained by reaction of the vinyl groups of the monomer in the solid content in the composition A is 70% by mass or more.

[Synthesis Example 2]
1 g of exemplified compound (Id) (manufactured by Aldrich) was added to 52.8 g of butyl acetate. While heating and refluxing (internal temperature 127 ° C.) in a nitrogen stream, a solution obtained by diluting 4 mg of V-601 (10-hour half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. with 4 ml of butyl acetate as a polymerization initiator for 2 hours The solution was added dropwise, and after completion of the addition, the mixture was heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 10 ml of tetrahydrofuran, and 1.8 ml of water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 10 ml of methanol was added. The solid content was collected by filtration and dried to obtain 0.49 g of a solid content. When the solid content was analyzed by GPC, components having a molecular weight larger than that of the exemplary compound (Id) were Mw = 1580 thousand, M _{z + 1} = 310,000, and Mn = 89,000. The unreacted exemplary compound (Id) was 3% by mass or less in the solid. No component with a molecular weight of 3 million or more was contained. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerization of the vinyl group and the remaining proton peak derived from the vinyl group were integrated at 48:52. The ratio was observed and it was found that vinyl groups were polymerized.
When 0.3 ml of this composition was added with 5 ml of a coating solvent (described in Table 1) and stirred at 40 ° C. for 3 hours, it was uniformly dissolved to obtain Composition B of the present invention.
From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomers in the solid content in the composition is 70% by mass or more.

[Synthesis Example 3]
1 g of exemplified compound (Id) (manufactured by Aldrich) was added to 26.4 g of butyl acetate. While heating and refluxing (internal temperature 127 ° C.) in a nitrogen stream, a solution obtained by diluting 2 mg of V-601 (10 hours half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries as a polymerization initiator with 2 ml of butyl acetate is taken over 2 hours. The mixture was added dropwise, and heated to reflux for 1 hour after the completion of the addition. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 15 ml of tetrahydrofuran, and 6 ml of water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 10 ml of methanol was added. The solid content was collected by filtration and dried to obtain 0.60 g of solid content. When the solid content was analyzed by GPC, the parts having a molecular weight larger than that of the compound (Id) were Mn = 34,000, Mw = 118,000, and M _{z + 1} = 270,000. The unreacted exemplary compound (Id) was 3% by mass or less in the solid. No component with a molecular weight of 3 million or more was contained. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerization of the vinyl group and the proton peak derived from the remaining vinyl group were integrated at 42:58. The ratio was observed and it was found that vinyl groups were polymerized.
When 5 ml of a coating solvent (described in Table 1) was added to 0.3 g of this composition and stirred at 40 ° C. for 3 hours, it was uniformly dissolved to obtain Composition C of the present invention.
From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomers in the solid content in the composition is 70% by mass or more.

[Synthesis Example 4]
1 g of exemplified compound (Id) (manufactured by Aldrich) was added to 13.2 g of butyl acetate. In a nitrogen stream, heating and refluxing (internal temperature 127 ° C.), a solution obtained by diluting 1 mg of V-401 (10 hours half-life temperature 88 ° C.) manufactured by Wako Pure Chemical Industries as a polymerization initiator with 1 ml of butyl acetate is taken over 2 hours. The mixture was added dropwise, and heated to reflux for 1 hour after completion of the addition. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 10 ml of tetrahydrofuran, and 1.8 ml of water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 10 ml of methanol was added. The solid content was collected by filtration and dried to obtain 0.41 g of solid content. When the solid content was analyzed by GPC, the components having a molecular weight larger than that of the compound (Id) were Mw = 12.8 million, M _{z + 1} = 380,000, and Mn = 31,000. The unreacted exemplary compound (Id) was 3% by mass or less in the solid. No component with a molecular weight of 3 million or more was contained. When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an integral ratio of a proton peak derived from an alkyl group obtained by polymerization of a vinyl group and a proton peak 53:47 derived from the remaining vinyl group was obtained. It was observed that the vinyl groups were polymerized.
When 5 ml of a coating solvent (described in Table 1) was added to 0.3 g of this composition and stirred at 40 ° C. for 3 hours, it was uniformly dissolved to obtain Composition D of the present invention.
From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomers in the solid content in the composition is 70% by mass or more.

[Synthesis Example 5]
H ₂ C═CH—Si (O _0.5 ) ₃ units of cage-like silsesquioxane, H ₂ C═CH—Si (O _0.5 ) ₃ units of 10 units of cage silsesquioxane and H _{2 C = CH-Si (O 0.5} ) 3 units 12 cage-like silsesquioxane mixtures San consisting (hybrid plastics Inc., model number: OL1170) 1g was added to ethyl acetate 361 g. In a nitrogen stream, 95 μl of Ruperox 11 manufactured by Arkema Yoshitosha was added as a polymerization initiator, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the solution was concentrated under reduced pressure to 2 g of liquid, 20 ml of methanol was added and stirred for 1 hour, and then the solid was collected by filtration and dried to obtain 0.83 g of solid content. When the solid content was analyzed by GPC, Mw = 1780,000 and Mn = 37,000. The unreacted starting material in the solid was 1% by mass or less. As GPC, Waters 2695 and Shodex GPC column KF-805L are used, column temperature is 40 ° C., tetrahydrofuran is used as an elution solvent at a flow rate of 1 ml / min, and a terahydrohydrofuran solution having a sample concentration of 0.5 mass%. Was injected. A monomer calibration curve was created using the integrated value of the RI detector (Waters 2414), and the monomer in the solid content was quantified. Mn and Mw were calculated using a calibration curve prepared using standard polystyrene.
When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerizing the vinyl group and the remaining proton peak derived from the vinyl group had an integration of 43:57. The ratio was observed and it was found that vinyl groups were polymerized.
When 0.3 ml of this composition was added with 5 ml of a coating solvent (described in Table 1) and stirred at 40 ° C. for 3 hours, it was uniformly dissolved.
Furthermore, 5 μl of BYK306 (manufactured by Big Chemie) was added as a surfactant to obtain Composition E of the present invention.
From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomer in the solid content in the composition E is 60% by mass or more.

[Synthesis Example 6]
1 g of exemplary compound (Id) was added to 361 g of ethyl acetate, and the mixture was heated to reflux in a nitrogen stream. A total of 6 μl of 2 μl of Lupelox 11 manufactured by Arkema Yoshitake Co., Ltd. was added every 2 hours as a polymerization initiator, and the mixture was further heated to reflux for 4 hours. Next, the mixture was cooled to room temperature and concentrated under reduced pressure to a liquid weight of 1.5 g. After adding 20 ml of methanol and stirring for 1 hour, the solid was collected by filtration and dried to obtain 0.87 g of a solid content. When the solid content was analyzed by GPC, Mw = 1780,000 and Mn = 35,000. The solid content did not substantially contain a component having a molecular weight of 2 million or more. The unreacted exemplary compound (Id) in the solid was 1% by mass or less.
Exemplified compound has about 20 mole% residual vinyl groups contained in (I-d), also the solids, ¹ HNMR- spectrum is solid ethyl acetate to about 6% by weight are attached It was possible to quantify from.
When 0.3 ml of this composition was added with 5 ml of a coating solvent (described in Table 1) and stirred at 40 ° C. for 3 hours, it was uniformly dissolved. Further, 5 μl of BYK 306 (manufactured by Big Chemie) and a surfactant were added to obtain Composition F of the present invention.

The composition prepared according to the above synthesis example was washed with propylene glycol methyl ether acetate (PGMEA), cyclohexanone and a mixture thereof as a cleaning solution, and the outermost peripheral shape was evaluated.
The compositions A to F prepared in the above synthesis examples are filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm, applied onto a 4-inch silicon wafer by a spin coating method, and then coated with a ACT series manufactured by Tokyo Electron. Formation and edge cleaning were performed. Also, the coating and cleaning processes in each example were all the same.
The film thickness and edge bulge were evaluated by the ratio (B / A) of the height (B) of the edge part to the film thickness (A) with a stylus type step gauge P-15 manufactured by KLATencor. The dielectric constant was measured using a mercury probe manufactured by Four Dimensions Inc. (measurement temperature 25 ° C.). Propylene glycol methyl ether acetate and cyclohexanone were used as the cleaning liquid. The evaluation results are shown in Table 1.

However, PGMEA / cyclohexanone is a mixed solvent of PEGMEA and cyclohexanone having a weight ratio of 15/85, and PGME / cyclohexanone is a mixed solvent of PEGME and cyclohexanone having a weight ratio of 25/75.
Surface tension ratio = surface tension of coating solvent / surface tension of cleaning solution

  From the results shown in Table 1, it can be seen that when the composition of the present invention is used and a solvent having a surface tension smaller than that of the cleaning liquid is used, a low dielectric constant film having a good coated surface can be formed.

Claims (2)

  A film is prepared by applying a composition obtained by dissolving a polymer compound obtained by polymerizing a cage-type silsesquioxane compound having two or more unsaturated groups as substituents in an organic solvent onto a substrate using a spin coater and drying the composition. An insulating film of a semiconductor device formed by forming a structure and removing an outer peripheral portion of the film structure with a cleaning liquid, wherein a surface tension of the organic solvent is equal to or less than a surface tension of the cleaning liquid Insulation film for semiconductor devices.   2. The semiconductor device insulating film according to claim 1, wherein the cleaning liquid is a ketone-based or ester-based solvent.